Resin structure

ABSTRACT

Provided is a thermoplastic resin structure formed of a resin composition that comprises substantially (a) from 5 to 80% by volume of a polyolefin resin and (b) from 20 to 95% by volume of a polyphenylene sulfide resin, which is characterized in that, in morphology therein seen through electronic microscopy, the polyphenylene sulfide resin (b) forms a matrix phase (continuous phase) and the polyolefin resin (a) forms a disperse phase. The thermoplastic resin structure gives plastic containers, tubes and their Attached parts having good barrier properties, strength, durability and workability.

TECHNICAL FIELD

[0001] The present invention relates to resin structures of good vaporand/or liquid transmission resistance, and their use. In particular, theinvention relates to resin moldings of specific transmission resistanceand workability, which are obtained by forming a specific morphology ofpolyolefin resin and polyphenylene sulfide resin (hereinafter referredto as PPS resin) and are favorable for vapor and/or liquid barrierarticles, to such resin structures favorable for containers and pipesfor storage and transportation of liquid chemicals such as oil andgasoline, to those favorable for wrapping and packaging materials andcontainers for foods and medicines, and to their use.

BACKGROUND ART

[0002] Polyolefin resins such as polyethylene and polypropylene are themost popular plastics that are widely used for daily necessaries, toys,machine parts, electric and electronic parts, and automobile parts. Therecent requirement increasing in the art is for gas-barrier(transmission-resistant) resin articles capable of preventing thecontents from leaking out and protecting them from the open air forensuring the safety and the storage stability of the contents and forprotecting the environment from pollution. However, since polyolefinresins are poorly resistant to liquid chemical and vapor transmissionthrough them, their use is often limited, and it is desired to improvethem.

[0003] For improving for the physical properties of such polyolefinresins, resin compositions and moldings consisting of polyolefin resinand polyamide resin of good transmission resistance have heretofore beenproposed in the art. The method could improve the transmissionresistance of the resin compositions and moldings over that of moldingsof polyolefin resin alone, but is still unsatisfactory. Thereforedesired is a technique of further improving the transmission resistanceof polyolefin resin structures.

[0004] For fuel tanks and oil tanks for automobiles, converting metalliccontainers into plastic containers is now actively investigated, asplastics are lightweight and easy to mold and work, their designlatitude is broad, and they are easy to handle. The matter of importancewith such plastic containers is that they do not leak the contents andcan protect the contents from the open air for ensuring the safety andthe storage stability of the contents and for protecting the environmentfrom pollution. Polyethylene, polypropylene and other polyolefincontainers are the most popular plastic containers, but their barrierproperties against gasoline and other specific oils are unsatisfactory.Therefore, it is difficult to directly use them for fuel tanks and oiltanks for automobiles. For such use, in general, they are worked intomulti-layer structures by coating them with a barrier layer of resin ofhigh transmission resistance.

[0005] One typical example of the resin to form such a barrier layer ispolyamide resin (for example, as in JP-A 220738/1983). However, therecent tendency in the field of automobile fuel is being toward using amixture of gasoline and alcohol, gasohol, for which the plasticcontainers obtainable in the above-mentioned prior art areunsatisfactory in point of their barrier properties. Therefore desiredis a technique of further improving the barrier properties of plasticcontainers.

[0006] On the other hand, it is known that PPS resin has extremely goodbarrier properties against liquid chemicals such as gasoline andautomobile oil, and against water and carbon dioxide. Blow-moldedcontainers and tubular structures of such PPS resin (for example, as inJP-A 90216/1987, 255832/1986, 32816/1991), and multi-layer structureswith a barrier layer formed of a specific PPS resin and a modifiedpolyolefin (for example, as in JP-A 190980/1994) have been proposed.However, since its interlayer adhesiveness to other resin is poor, PPSresin has some problems in that its coextrusion and lamination withother resin materials such as polyethylene, polypropylene and otherpolyolefins is difficult and its main component must be an expensivespecific PPS resin. For these reasons, the application range of PPSresin is limited.

[0007] The present invention is to improve the transmission resistanceof polyolefin resin, and its object is to provide resin structures ofspecifically improved liquid chemical and vapor transmission resistance,not detracting from the properties such as toughness, moldability andworkability intrinsic to polyolefin resin, especially to providepolyolefin-PPS resin structures favorable for vapor and/or liquidbarrier articles, and to provide multi-layer structures of goodtransmission resistance, moldability, workability, interlayeradhesiveness and toughness that are favorable to plastic containers andcan be stably and economically formed into good plastic containers.

DISCLOSURE OF THE INVENTION

[0008] We, the present inventors have studied to solve the problemsnoted above, and, as a result, have found that, when a polyolefin resinand a PPS resin are mixed in a specific ratio optionally along with aninorganic filler in such a controlled manner that the PPS resin phase inmorphology in the resulting resin composition could form a dispersedconfiguration capable of being a continuous phase or a laminar (layered)phase in the shaped structure of the resin composition, then theabove-mentioned problems can be solved. On the basis of this finding, wehave reached the present invention.

[0009] Specifically, the invention provides the following:

[0010] (1) A thermoplastic resin structure formed of a resin compositionthat comprises substantially (a) from 5 to 80% by volume of a polyolefinresin and (b) from 20 to 95% by volume of a polyphenylene sulfide resin,which is characterized in that, in morphology therein seen throughelectronic microscopy, the polyphenylene sulfide resin (b) forms amatrix phase (continuous phase) and the polyolefin resin (a) forms adisperse phase;

[0011] (2) The thermoplastic resin structure of above (1), for which theblend ratio of the polyolefin resin (a) and the polyphenylene sulfideresin (b) is such that the former accounts for from 55 to 80% by volumeand the latter for from 20 to 45% by volume;

[0012] (3) The thermoplastic resin structure of above (1), for which theblend ratio of the polyolefin resin (a) and the polyphenylene sulfideresin (b) is such that the former accounts for from 60 to 75% by volumeand the latter for from 25 to 40% by volume;

[0013] (4) A thermoplastic resin structure formed of a resin compositionthat comprises (a) from 15 to 85% by volume of a polyolefin resin and(b) from 15 to 85% by volume of a polyphenylene sulfide resin, which ischaracterized in that, in morphology therein seen through electronicmicroscopy, both the phase of the polyphenylene sulfide resin (b) andthe phase of the polyolefin resin (a) are substantially continuousphases;

[0014] (5) A thermoplastic resin structure formed of a resin compositionthat comprises (a) from 55 to 95% by volume of a polyolefin resin and(b) from 5 to 45% by volume of a polyphenylene sulfide resin, which ischaracterized in that, in morphology therein seen through electronicmicroscopy, the polyolefin resin. (a) forms a continuous phase and thepolyphenylene sulfide resin (b) forms a laminar disperse phase;

[0015] (6) The thermoplastic resin structure of any of (1) to (5), forwhich the polyolefin resin (a) is at least one selected frompolyethylene, polypropylene, ethylene/α-olefin copolymers, [copolymersof (ethylene and/or propylene) and (unsaturated carboxylic acid and/orunsaturated carboxylate)], and [copolymers of (ethylene and/orpropylene) and (unsaturated carboxylic acid and/or unsaturatedcarboxylate) in which at least a part of the carboxyl groups aremodified into metal salts];

[0016] (7) The thermoplastic resin structure of any of (1) to (6), whichcontains (c) from 0.5 to 200 parts by weight, relative to 100 parts byweight of the total of the polyolefin resin (a) and the polyphenylenesulfide resin (b), of an inorganic filler;

[0017] (8) Containers for transportation or storage of liquid chemicalsor gases, which are obtained by working the thermoplastic resinstructure of any of (1) to (7);

[0018] (9) Attached parts for containers for transportation or storageof liquid chemicals or gases, which are obtained by working thethermoplastic resin structure of any of (1) to (7);

[0019] (10) Moldings of the thermoplastic resin structure of any of (1)to (7), which are formed in at least one method of injection molding,injection compression molding or compression molding;

[0020] (11) A multi-layer structure with a barrier layer, in which thebarrier layer is formed of the thermoplastic resin structure of any of(1) to (7);

[0021] (12) The multi-layer structure of (11), wherein a neighboringlayer is formed on one or both surfaces of the barrier layer, and theneighboring layer is a thermoplastic resin layer differing from thethermoplastic resin structure that forms the barrier layer;

[0022] (13) The multi-layer structure of (12), wherein the thermoplasticresin to form the neighboring layer is at least one selected frompolyolefin resins, thermoplastic polyester resins, polyamide resins,polycarbonate resins and ABS resins;

[0023] (14) The multi-layer structure of (12), wherein the thermoplasticresin to form the neighboring layer is at least one selected frompolyolefin resins, thermoplastic polyester resins and polyamide resins;

[0024] (15) The multi-layer structure of (12), wherein the thermoplasticresin to form the neighboring layer is an ethylene homopolymer and/or anethylene/α-olefin copolymer having a melt flow rate of from 0.01 to 30g/10 min and a density of from 0.90 to 0.97 g/cm³;

[0025] (16) The multi-layer structure of (12), which has an adhesivelayer formed between the barrier layer and the neighboring layer;

[0026] (17) The multi-layer structure of (16), wherein the adhesivelayer is formed of a modified polyolefin having a degree ofcrystallinity of at most 50% and containing from 0.01 to 10% by weightof an unsaturated carboxylic acid or its derivative grafted thereon;

[0027] (18) The multi-layer structure of (17), wherein the adhesivelayer comprises from 60 to 99 parts by weight of a modified polyolefinhaving a degree of crystallinity of at most 50% and containing from 0.01to 10% by weight of an unsaturated carboxylic acid or its derivativegrafted thereon, and from 1 to 40 parts by weight of a tackifier;

[0028] (19) The multi-layer structure of any of (11) to (18), which isformed through coextrusion;

[0029] (20) The multi-layer structure of any of (11) to (19), which isformed into multi-layered tubes or multi-layered blow moldings throughcoextrusion.

BRIEF DESCRIPTION OF THE DRAWINGS

[0030]FIG. 1 shows a model of the morphology of a resin structure inwhich the continuous phase is formed of a PPS resin component (PPS) andthe disperse phase is formed of a polyolefin resin component (PO).

[0031]FIG. 2 shows a model of the morphology of a resin structure inwhich a PPS resin component and a polyolefin resin component both formsubstantially continuous phases.

[0032]FIG. 3 shows a model of the morphology of a resin structure inwhich the continuous phase is formed of a polyolefin resin component andthe disperse phase is formed of a large number of thin, two-dimensionallaminae (layers) of a PPS resin component.

[0033]FIG. 4 is an electronmicroscopic picture showing the morphology ofthe resin structure obtained in Example 8, in which the dark part isformed of a polyolefin resin component.

[0034]FIG. 5 is an electronmicroscopic picture showing the morphology ofthe resin structure obtained in Comparative Example 1, in which the darkpart is formed of a polyolefin resin component.

BEST MODES OF CARRYING OUT THE INVENTION

[0035] Embodiments of the invention are described below. “Weight”referred to herein means “mass”.

[0036] The polyolefin resin (a) for use in the invention is athermoplastic resin prepared through polymerization or copolymerizationof olefins such as ethylene, propylene, butene, isoprene, and pentene.Concretely, it includes homopolymers such as polyethylene,polypropylene, polystyrene, polyacrylate, polymethacrylate,poly-1-butene, poly-1-pentene, polymethylpentene; as well asethylene/α-olefin copolymers, vinyl alcohol ester homopolymers, polymersprepared by at least partially hydrolyzing vinyl alcohol esterhomopolymers, [polymers obtained by at least partially hydrolyzingcopolymers of (ethylene and/or propylene) and vinyl alcohol ester],[copolymers of (ethylene and/or propylene) and (unsaturated carboxylicacid and/or unsaturated carboxylate)], [copolymers of (ethylene and/orpropylene) and (unsaturated carboxylic acid and/or unsaturatedcarboxylate) in which at least a part of the carboxyl groups aremodified into metal salts], block copolymers of conjugated diene andvinyl-aromatic hydrocarbon, and hydrogenated derivatives of the blockcopolymers.

[0037] Of those, preferred are polyethylene, polypropylene,ethylene/α-olefin copolymers, [copolymers of (ethylene and/or propylene)and (unsaturated carboxylic acid and/or unsaturated carboxylate)], and[copolymers of (ethylene and/or propylene) and (unsaturated carboxylicacid and/or unsaturated carboxylate) in which at least a part of thecarboxyl groups are modified into metal salts]; and more preferred arelow-, middle- and high-density polyethylene, polypropylene, andethylene/α-olefin copolymers.

[0038] Polypropylene for use herein is not specifically defined, and maybe any of isotactic, atactic or syndiotactic polypropylene. Apart fromsuch homopolymers, also usable in the invention are block or randomcopolymers comprising at least 70% by weight of a propylene componentand containing some other olefin component.

[0039] Ethylene/α-olefin copolymers for use in the invention arecopolymers of ethylene and at least one α-olefin having from 3 to 20carbon atoms, in which, concretely, the α-olefin having from 3 to 20carbon atoms includes propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene,3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene,4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene,4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene,11-methyl-1-dodecene, 12-ethyl-1-tetradecene, and their combinations. Ofthose, preferred are α-olefins having from 3 to 12 carbon atoms, as themechanical strength of the copolymers comprising any of them is high.The α-olefin content of the ethylene/α-olefin copolymer preferably fallsbetween 1 and 30 mol %, more preferably between 2 to 25 mol %, even morepreferably between 3 and 20 mol %.

[0040] The copolymers may be further copolymerized with at least onenon-conjugated diene such as 1,4-hexadiene, dicyclopentadiene,2,5-norbornadiene, 5-ethylidenenorbornene, 5-ethyl-2,5-norbornadiene,5-(1′-propenyl)-2-norbornene.

[0041] The unsaturated carboxylic acid in the [copolymers of (ethyleneand/or propylene) and (unsaturated carboxylic acid and/or unsaturatedcarboxylate)] is any of acrylic acid or methacrylic acid or theirmixture; and the unsaturated carboxylate therein includes, for example,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl anddecyl esters of such unsaturated carboxylic acids, and their mixtures.Especially preferred are ethylene/methacrylic acid copolymers, andethylene/methacrylic acid/acrylate copolymers.

[0042] Preferably, the melt flow rate (hereinafter referred to as MFR,under ASTM D1238) of the polyolefin resin (a) for use in the inventionfalls between 0.01 and 70 g/10 min, more preferably between 0.03 and 60g/10 min. If its MFR is lower than 0.01 g/10 min, the resin isunfavorable since its flowability is not low; but if higher than 70 g/10min, the resin is also unfavorable since its mechanical strength is low.The polyolefin resin of which the MFR falls within the preferred rangemay also be one prepared by thermally decomposing a polymerizedpolyolefin resin with an organic peroxide.

[0043] The method of preparing the polyolefin resin (a) for use in theinvention is not specifically defined, for which, for example,employable is any of radical polymerization, coordination polymerizationwith a Ziegler-Natta catalyst, anionic polymerization, or coordinationpolymerization with a metallocene catalyst.

[0044] Preferably, the polyolefin resin (a) for use in the invention ismodified with at least one compound selected from unsaturated carboxylicacids or their derivatives. The modified polyolefin resin is highlymiscible with other resin, and has the ability to well control theseparated morphology in the resulting resin composition, and, as aresult, the transmission resistance of the resin structure is improved.Using the modified polyolefin resin is one preferred embodiment of theinvention.

[0045] Examples of the unsaturated carboxylic acids or their derivativesthat serve as the modifying agent are acrylic acid, methacrylic acid,maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleicacid, methylfumaric acid, mesaconic acid, citraconic acid, glutaconicacid, and metal salts of these carboxylic acids; and methylhydrogenmaleate, methyl hydrogenitaconate, methyl acrylate, ethylacrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate,methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethylmethacrylate, aminoethyl methacrylate, dimethyl maleate, dimethylitaconate, maleic anhydride, itaconic anhydride, citraconic anhydride,endobicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic acid,endobicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic acid anhydride,maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide,glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate,glycidyl itaconate, glycidyl citraconate, and5-norbornene-2,3-dicarboxylic acid. Of those, preferred are unsaturateddicarboxylic acids and their anhydrides; and especially preferred aremaleic acid and maleic anhydride.

[0046] The method of introducing such an unsaturated carboxylic acid orits derivative component into polyolefin resin is not specificallydefined. For example, the essential ingredient, olefin compound may becopolymerized with an unsaturated carboxylic acid or its derivativecompound; or a non-modified polyolefin resin may be grafted with anunsaturated carboxylic acid or its derivative compound in the presenceof a radical initiator. In any of such methods, the acid or derivativecomponent may be introduced into polyolefin resin. The amount of theunsaturated carboxylic acid or its derivative component to be introducedinto polyolefin preferably falls between 0.001 and 40 mol %, morepreferably between 0.01 and 35 mol % of all the olefin monomers thatconstitute the modified polyolefin.

[0047] The PPS resin (b) for use in the invention is a polymer havingrepetitive units of the following structural formula (I):

[0048] From the viewpoint of its heat resistance, the polymer preferablycontains at least 70 mol % more preferably at least 90 mol % of therepetitive units of the structure formula. The PPS resin may contain anyother repetitive units such as those mentioned below, within a rangesmaller than 30 mol % of all the repetitive units that constitute theresin.

[0049] The PPS polymer partly having the structure as above will have alowered melting point. Therefore, in case where the melting point of thethermoplastic resin not in the barrier layer of the multi-layerstructure of the invention Is low, the PPS resin of the type isadvantageous in point of its moldability.

[0050] The melt viscosity of the PPS resin for use in the invention isnot specifically defined, so far as the resin can be kneaded in melt. Ingeneral, it falls between 50 and 20000 poises (at 320° C. at a shearrate of 1000 sec⁻¹), more preferably between 100 and 5000 poises.

[0051] The PPS resin of the type can be prepared in any known method,for example, according to the method for preparing polymers having arelatively small molecular weight, described in JP-B 3368/1970; or themethod for preparing polymers having a relatively large molecularweight, described in JP-B12240/1977 and JP-A 7332/1986. Needless-to-say,the PPS resin prepared in the manner as above for use in the inventionmay be processed in various methods. For example, it may be heated inair for crosslinking it and/or increasing its molecular weight; or maybe heated in an inert gas atmosphere such as nitrogen or under reducedpressure; or may be washed with any of organic solvents, hot water oraqueous acid solutions; or may be activated with any of functionalgroup-having compounds such as acid anhydrides, amines, isocyanates andfunctional group-having disulfide compounds.

[0052] One concrete method of heating the PPS resin for crosslinking itand/or increasing its molecular weight comprises heating it in anoxidizing gas atmosphere such as air or oxygen or in a mixed gasatmosphere comprising the oxidizing gas and an inert gas such asnitrogen or argon, in a container heated at a predetermined temperatureso that its melt viscosity reaches the desired level. The temperaturefor the heat treatment generally falls between 170 and 280° C., butpreferably between 200 and 270° C. The time for the heat treatmentgenerally falls between 0.5 and 100 hours, but preferably between 2 and50 hours. By controlling both the two, the melt viscosity of the resincan reach the desired level. The device for the heat treatment may beany ordinary hot air drier or may be a rotary heating device or aheating device equipped with a stirring blade. For efficiently and moreuniformly heating the resin therein, preferred is a rotary heatingdevice or a heating device equipped with a stirring blade.

[0053] One concrete method of heating the PPS resin in an inert gasatmosphere such as nitrogen or under reduced pressure comprises heatingit in an inert gas atmosphere such as nitrogen or under reducedpressure, at a temperature falling between 150 and 280° C., preferablybetween 200 and 270° C., for a period of time falling between 0.5 and100 hours, preferably between 2 and 50 hours. The device for the heattreatment may be any ordinary hot air drier or may be a rotary heatingdevice or a heating device equipped with a stirring blade. Forefficiently and more uniformly heating the resin therein, preferred is arotary heating device or a heating device equipped with a stirringblade.

[0054] Preferably, the PPS resin for use in the invention is deionized.For deionizing it, concretely, the resin may be washed with any ofaqueous acid solutions, hot water, or organic solvents. Two or morethese treatments may be combined.

[0055] One concrete method of washing the PPS resin with an organicsolvent is described. The organic solvent to be used for washing theresin is not specifically defined, and may be any and every one nothaving the function of decomposing the PPS resin. For example, itincludes nitrogen-containing polar solvents such as N-methylpyrrolidone,dimethylformamide, dimethylacetamide; sulfoxide or sulfone solvents suchas dimethyl sulfoxide, dimethyl sulfone; ketone solvents such asacetone, methyl ethyl ketone, diethyl ketone, acetophenone; ethersolvents such as dimethyl ether, dipropyl ether, tetrahydrofuran;halogen-containing solvents such as chloroform, methylene chloride,trichloroethylene, dichloroethylene, dichloroethane, tetrachloroethane,chlorobenzene; alcohol or phenol solvents such as methanol, ethanol,propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol,cresol, polyethylene glycol; and aromatic hydrocarbon solvents such asbenzene, toluene, xylene. Of those organic solvents, preferred areN-methylpyrrolidone, acetone, dimethylformamide, and chloroform. One ormore such organic solvents may be used either singly or as combined. Forwashing the PPS resin with such an organic solvent, for example, theresin may be dipped in the solvent, optionally stirred or heatedtherein. The temperature at which the PPS resin is washed with such anorganic solvent is not specifically defined, generally falling betweenroom temperature and 300° C. or so. The washing efficiency is higher ata higher washing temperature, but, in general, temperatures fallingbetween room temperature and 150° C. or so are enough for good washingresults. After thus washed with such an organic solvent, the PPS resinis preferably washed a few times with water or warm water to remove theorganic solvent remaining in the resin.

[0056] One concrete method of washing the PPS resin with hot water isdescribed. For the desired chemical change in the PPS resin washed withhot water, the water to be used is preferably distilled water ordeionized water. Concretely, in general, a predetermined amount of thePPS resin is put into a predetermined amount of water, and heated undernormal pressure or in a pressure container with stirring. Regarding theratio of the PPS resin to water, it is desirable that the amount ofwater is larger than that of the resin. In general, the bath ratio is soselected that at most 200 g of the PPS resin is put in one liter ofwater.

[0057] One concrete method of processing the PPS resin with acid isdescribed. For example, the PPS resin is dipped in acid or an aqueoussolution of acid, optionally stirred or heated. The acid to be used isnot specifically defined, so far as it does not decompose the PPS resin.For example, it includes aliphatic saturated monocarboxylic acids suchas formic acid, acetic acid, propionic acid, butyric acid;halo-substituted, aliphatic saturated carboxylic acids such aschloroacetic acid, dichloroacetic acid; aliphatic unsaturatedmonocarboxylic acids such as acrylic acid, crotonic acid; aromaticcarboxylic acids such as benzoic acid, salicylic acid; dicarboxylicacids such as oxalic acid, malonic acid, succinic acid, phthalic acid,fumaric acid; inorganic acidic compounds such as sulfuric acid,phosphoric acid, hydrochloric acid, carbonic acid, silicic acid. Ofthose, preferred are acetic acid and hydrochloric acid. Theacid-processed PPS resin is preferably washed a few times with water orwarm water for removing the acid or salt remaining in the resin. Thewater to be used for the washing treatment is preferably distilled wateror deionized water not interfering with the desirable chemical change inthe acid-processed PPS resin.

[0058] The resin composition of the invention may additionally containany known compatibilizer having the function of improving themiscibility of the polyolefin resin (a) and the PPS resin (b) thatconstitute the resin composition. Examples of the compatibilizer areorganosilane compounds such as alkoxysilanes having at least onefunction group selected from an epoxy group, an amino group, anisocyanate group, a hydroxyl group, a mercapto group and an ureidogroup; modified polyolefins such as random, block or graft copolymers ofα-olefins, e.g., ethylene or propylene, with at least one compoundselected from α,β-unsaturated carboxylic acids, e.g., acrylic acid,methacrylic acid, maleic acid or crotonic acid, or their derivatives,e.g., esters, anhydrides, halides or salts with sodium, potassium,magnesium or zinc; and epoxy group-having olefin copolymers such asthose comprising, as the essential ingredients, α-olefins and glycidylesters of α,β-unsaturated acids, as well as other polyfunctional epoxycompounds. Two or more of these may be combined for use herein.

[0059] The thermoplastic resin structure of the invention ischaracterized by its partial or entire morphology of such that (1) a PPSresin component forms a continuous phase (matrix phase) and a polyolefinresin component forms a disperse phase (for example, like a sea-islandconfiguration), or (2) a PPS resin component and a polyolefin resincomponent both form substantially continuous phases (for example, like asea-sea configuration), or (3) the continuous phase is formed of apolyolefin resin component and the disperse phase is formed of a largenumber of thin, two-dimensional laminae (layers) of a PPS resincomponent (like a laminar configuration). The shape of the structure isnot specifically defined. In different sites of the structure, themorphology (1), (2) or (3) may be present together, or may appear twiceor more. The morphology (1), (2) or (3) can be seen and confirmedthrough scanning or transmission electronic microscopy.

[0060] The blend ratio of the polyolefin resin (a) and the PPS resin (b)that constitute the thermoplastic resin structure of the invention isdescribed. In case where the PPS resin component forms a continuousphase (matrix phase) and the polyolefin resin component forms a dispersephase in the morphology of the structure (for example, like a sea-islandconfiguration as in FIG. 1), the polyolefin resin accounts for from 5 to80% by volume and the PPS resin for from 20 to 95% by volume.Preferably, the polyolefin resin accounts for from 55 to 80% by volumeand the PPS resin for from 20 to 45% by volume. In that case where theamount of the PPS resin component is small, the morphology in which thePPS resin forms a continuous phase can be formed, for example, bysuitably controlling the melt viscosity ratio of polyolefin resin/PPSresin. The moldings having the morphology have a good balance of wetcharacteristics and transmission resistance and, when they are used forthe barrier layer in multi-layer structures, they also have a goodbalance of toughness, interlayer adhesiveness, barrier properties andcost. Therefore, they are extremely favorable. More preferably, theblend ratio of the two components is such that the polyolefin resinaccounts for from 60 to 75% by volume and the PPS resin for from 25 to40% by volume. If the polyolefin resin component (a) is larger than 80%by volume, the PPS resin component could hardly form the continuousphase characteristic of the resin moldings of the invention, and theobject of the invention cannot be attained. On the other hand, if thepolyolefin resin component (a) is smaller than 5% by volume, it isunfavorable since the resin moldings could not be tough and themulti-layer structures could not have good interlayer adhesiveness.

[0061] In case where the PPS resin component and the polyolefin resincomponent both form substantially continuous phases (matrix phases) inthe morphology of the resin structure (for example, like a sea-seaconfiguration as in FIG. 2), it is important that the melt viscosity andthe compatibility of the polyolefin resin and the PPS resin arecontrolled within a composition range of such that the polyolefin resinaccounts for from 15 to 85% by volume and the PPS resin for from 15 to85% by volume. For embodying the separated morphology in that manner,the blend ratio of the two components is preferably such that thepolyolefin resin accounts for from 30 to 70% by volume and the PPS resinfor from 30 to 70% by volume, more preferably such that the polyolefinresin accounts for from 35 to 65% by volume and the PPS resin for from35 to 65% by volume. If the polyolefin resin component (a) is largerthan 85% by volume, the PPS resin component could hardly form asubstantially continuous phase, and structures that attain the object ofthe invention could not be obtained.

[0062] For forming the morphology in which the polyolefin resincomponent forms a continuous phase (matrix phase) and the PPS resincomponent forms a large number of thin, two-dimensional laminae (layers)of a disperse phase (a laminar structure as in FIG. 3), the polyolefinresin accounts for from 55 to 95% by volume and the PPS resin for from 5to 45% by volume. Preferably, the polyolefin resin accounts for from 60to 90% by volume and the PPS resin for from 10 to 40% by volume; morepreferably, the polyolefin resin accounts for from 65 to 85% by volumeand the PPS resin for from 15 to 35% by volume. If the polyolefin resincomponent (a) is larger than 95% by volume, the laminar disperse phaseof the PPS resin component could not be prolonged to have a desiredlength and a desired weight, and the object of the invention cannot beattained. If the polyolefin resin component (a) is smaller than 55% byvolume, the PPS resin component could hardly form a laminar dispersephase.

[0063] L/T (length/thickness) of the PPS resin component that forms thelaminar disperse phase is preferably at least 30. More preferably, L/Tis at least 100, even more preferably at least 150. If L/T is smallerthan 30, structures having the desired barrier properties could not beobtained. The uppermost limit of L/T is not specifically defined, but ispreferably at most 1×10⁶ in practical use.

[0064] The inorganic filler (c) usable in the invention is notspecifically defined, and may be any fibrous, tabular, powdery orgranular filler. Concretely, for example, it includes fibrous or whiskerfillers such as glass fibers, PAN or pitch-type carbon fibers, metalfibers, e.g., stainless steel fibers, aluminium fibers or brass fibers,organic fibers, e.g., aromatic polyamide fibers, and gypsum fibers,ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers, silicafibers, titanium oxide fibers, silicon carbide fibers, rock wool,potassium titanium whiskers, barium titanate whiskers, aluminium boratewhiskers, silicon nitride whiskers; and powdery, granular or tabularfillers such as mica, talc, kaolin, silica, calcium carbonate, glassbeads, glass flakes, glass microballoons, clay, molybdenum disulfide,wollastonite, titanium oxide, zinc oxide, calcium polyphosphate,graphite. Of those fillers, preferred are glass fibers, as well as PANcarbon fibers for electroconductive structures. The type of the glassfibers for use herein is not specifically defined, and may be any onesgenerally used for reinforcing resin. For example, they may be in anyform of long fibers or short fibers of chopped strands or milled fibers.As combined, two or more different types of fillers mentioned above maybe used herein. On its surface, the filler for use in the invention maybe processed with a known coupling agent (e.g., silane coupling agent,titanate coupling agent), or with any other surface-treating agent.Glass fibers serving as the filler may be coated or bundled withthermoplastic resin such as ethylene/vinyl acetate copolymer or withthermosetting resin such as epoxy resin.

[0065] The filler content of the resin composition preferably fallsbetween 0.5 and 200 parts by weight, more preferably between 5 and 200parts by weight, even more preferably between 10 and 150 parts by weightrelative to 100 parts by weight of the total of the polyolefin resin (a)and the PPS resin (b).

[0066] The multi-layer structure of the invention is formed bylaminating different types of resin layers, in which at least one layer(hereinafter referred to as a barrier layer (a)) is formed of thethermoplastic resin structure having the specific morphology as above,or a resin layer (hereinafter referred to as a neighboring layer (β))differing from the barrier layer is formed on at least one surface of alayer of the thermoplastic resin structure of the invention having adifferent composition or morphology (this is also a barrier layer) orthe barrier layer. In one preferred embodiment of the multi-layerstructure of the invention, an adhesive, co-extrudable resin layer(hereinafter referred to as an adhesive layer (γ)) is suitably formedbetween the barrier layer (a) and the neighboring layer (β) forenhancing the adhesiveness between the two layers. Concretely, forexample, the layer configuration of the multi-layer structure of thetype includes a two-resin two-layer configuration of layer (α)/layer(β): a two-rein three-layer configuration of layer (β)/layer (α)/layer(β); a three-resin three-layer configuration of layer (β)/layer(γ)/layer (α); a three-resin four-layer configuration of layer (β)/layer(γ) /layer (α)/layer (β); and a three-resin five-layer configuration oflayer (β)/layer (γ) layer (α)/layer (γ)/layer (β), to which, however,the invention is not limited.

[0067] The resin to form the neighboring layer (β) in the multi-layerstructure of the invention is a thermoplastic resin of which themorphology and the composition differ from the requirements in theinvention. The type of the thermoplastic resin is not specificallydefined, and may be any one selected in accordance with the use and theobject of the multi-layer structure. Its examples are saturatedpolyester resins, polysulfone resins, polyethylene tetrafluoride resins,polyetherimide resins, polyamidimide resins, polyamide resins, polyimideresins, polycarbonate resins, polyether sulfone resins, polyether ketoneresins, polythioether ketone resins, polyether-ether ketone resins,thermoplastic polyurethane resins, polyolefin resins, ABS resins,polyamide elastomers, and polyester elastomers. Two or more of these maybe combined for use herein. Of those, especially preferred arepolyolefin resins, thermoplastic polyester resins, polyamide resins,polycarbonate resins and ABS resins.

[0068] Preferred examples of the polyolefin resins may be the same asthose of the component (a) mentioned hereinabove. Above all, especiallypreferred are low-, middle- and high-density polyethylene,polypropylene, ethylene/α-olefin copolymer, poly-4-methylpentene-1,chloropolyethylene, and chloropolypropylene; and more preferred areethylene homopolymer and/or ethylene/α-olefin copolymer having a meltflow rate of from 0.01 to 30 g/10 min and a density of from 0.90 to 0.97g/cm³.

[0069] Preferred examples of the thermoplastic polyesters are thoseobtained from dicarboxylic acids such as terephthalic acid and aliphaticdiols. The dicarboxylic acids except terephthalic acid for thepolyesters are, for example, aliphatic dicarboxylic acids having from 2to 20 carbon atoms, such as azelaic acid, sebacic acid, adipic acid,decanedicarboxylic acid; aromatic dicarboxylic acids such as isophthalicacid, naphthalenedicarobxylic acid; and alicyclic dicarboxylic acidssuch as cyclohexanedicarboxylic acid. One or more of these may be usedeither singly or as combined. The aliphatic diols include, for example,ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,1,4-butanediol, trimethylene glycol, 1,4-cyclohexanedimethanol, andhexamethylene glycol. Concretely, the polyesters are polyethyleneterephthalate, polypropylene terephthalate, polybutylene terephthalate,polyhexamethylene terephthalate, polycyclohexylenedimethyleneterephthalate, and polyethylene naphthalate. Of those, especiallypreferred for use herein are polybutylene terephthalate of goodmechanical strength, and copolyesters that comprise a dicarboxylic acidcomponent containing at least 60 mol %, preferably at least 70 mol % ofterephthalic acid along with dodecanedicarboxylic acid and/orisophthalic acid, and a 1,4-butanediol component.

[0070] The degree of polymerization of these thermoplastic polyesterresins is not specifically defined. For example, polybutyleneterephthalate and copolyesters that are preferred for use in theinvention are preferably such that the intrinsic viscosity thereofmeasured in a 0.5% orthochlorophenol solution at 25° C. falls between0.5 and 2.5, more preferably between 0.8 and 2.0. Polyethyleneterephthalate for use herein is preferably such that its intrinsicviscosity measured in a 0.5% orthochlorophenol solution at 25° C. fallsbetween 0.54 and 1.5, more preferably between 0.6 and 1.2.

[0071] The polyamide resins preferred for use herein are, for example,those comprising, as the essential constituent components, amino acid,lactam or diamine, and dicarboxylic acid. Examples of the essentialconstituent components are amino acids such as 6-aminocaproic acid,1-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoicacid; lactams such as ε-caprolactam, (ω-laurolactam; aliphatic,alicyclic or aromatic diamines such as tetramethylenediamine,hexamethylenediamine, 2-methylpentamethylenediamine,nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine,2,2,4-/2,4,4-trimethylhexamethylenediamine,5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine,1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane,1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane,bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane,2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine,aminoethylpiperazine; and aliphatic, alicyclic or aromatic dicarboxylicacids such as adipic acid, suberic acid, azelaic acid, sebacic acid,dodecanedicarboxylic acid, terephthalic acid, isophthalic acid,2-chloroterephthalic acid, 2-methylterephthalic acid,5-methylisophthalic acid, 5-sodium-sulfoisophthalic acid,hexahydroterephthalic acid, hexahydroisophthalic acid. In the invention,nylon homopolymers or copolymers derived from these starting compoundsmay be used either singly or as combined.

[0072] Especially useful in the invention are heat-resistant and strongpolyamide resins having a melting point of not lower than 150° C.Concretely, they include polycapramide (nylon 6), polyundecanamide(nylon 11), polydodecanamide (nylon 12), polyhexamethylenadipamide(nylon 66), polycapramide/polyhexamethylenadipamide copolymer (nylon6/66), polytetramethylenadipamide (nylon 46),polyhexamethylenesebacamide (nylon 610), polyhexamethylenedodecamide(nylon 612), polyhexamethyleneterephthalamide/polycapramide copolymer(nylon 6T/6), polyhexamethylenadipamide/polyhexamethyleneterephthalamidecopolymer (nylon 66/6T),polyhexamethylenadipamide/polyhexamethylenisophthalamide copolymer(nylon 66/6I),polyhexamethylenadipamide/polyhexamethyleneterephthalamide/polyhexamethylenisophthalamidecopolymer (nylon 66/6T/6I),polyhexamethyleneterephthalamide/-polyhexamethylenisophthal amidecopolymer (nylon 6T/6I),polyhexamethyleneterephthalamide/polydodecanamide copolymer (nylon6T/12), polyhexamethyleneterephthalamide/poly(2-methylpentamethylene)terephthalamide copolymer (nylon 6T/M5T), polyxylylenadipamide (nylonXD6), polynonamethyleneterephthalamide (nylon 9T), and their mixturesand copolymers.

[0073] Especially preferred are copolymers havinghexamethyleneterephthalamide units, such as nylon 6, nylon 66, nylon 12,nylon 11, nylon 6/66 copolymer, nylon 610, nylon 6T/66 copolymer, nylon6T/6I copolymer, nylon 6T/6 copolymer. Also preferred in practical useare mixtures of these polyamide resins combined in accordance with thenecessary properties such as moldability, heat resistance and barrierproperties.

[0074] The degree of polymerization of the polyamide resins is notspecifically defined. For example, preferred are those having a relativeviscosity of from 2.0 to 7.0, more preferably from 2.5 to 6.0, measuredin a 98% concentrated sulfuric acid solution having a sampleconcentration of 0.01 g/ml at 25° C.

[0075] The thermoplastic resins to form the neighboring layer (β) maycontain, if desired, additives such as plasticizer, antioxidant,nucleating agent and colorant suitable to the respective resins.

[0076] The multi-layer structure of the invention, which has a barrierlayer (a) formed of the thermoplastic resin structure having a separatedmorphology specifically defined in the invention, and a neighboringlayer (β) formed on one or both surfaces of the barrier layer, can beproduced, for example, in a two-layer injection molding method. However,the multi-layer structure in the form of a film or sheet may be producedin a coextrusion molding method that comprises melting the layer-formingcompositions in separate extruders, feeding the melts into amultilayer-forming die and coextruding them through the die; or in alamination molding method that comprises separately forming a layer tobe the neighboring layer followed by melt-extruding a barrier layerthereon. The multi-layer structure for blow-molding containers such asbottles, barrels or tanks or for tabular articles such as pipes or tubesmay be produced in an ordinary coextrusion molding method. For example,two-layered blow moldings of the multi-layer structure, of which theinner layer is a barrier layer having a specific morphology as hereinand the outer layer is a neighboring layer, can be produced byseparately feeding a resin composition for the barrier layer and a resincomposition for the neighboring layer into the respective two extruders,then feeding the two resin melts into a die common thereto underpressure to form the respective circular flows integrated in such amanner that the flow for the barrier layer is inside and the flow forthe neighboring layer is outside, then coextruding them out of the die,and working the resulting laminate in an ordinary known tube-forming orblow-molding method to give the intended two-layered blow moldings.Three-layered blow moldings of the multi-layer structure can be producedin the same manner as above, but using three extruders to formthree-layered structures. For these, alternatively, usable are twoextruders to form two-resin three-layered blow moldings. Of thosemethods, preferred is the coextrusion molding method as it ensures goodinterlayer adhesiveness of the multi-layer structures produced therein.

[0077] Preferably, the multi-layer structure of the invention has anadhesive layer (γ) suitably formed between the barrier layer (α) and theneighboring layer (β) for the purpose of further improving the impactresistance, the moldability and the interlayer adhesiveness thereof. Theresin to form the adhesive layer is not specifically defined in point ofits configuration, so far as it is adhesive to both the barrier layer(α) and the neighboring layer (β) and it is coextrudable with the twolayers. Concretely, examples of the resin are modified polyolefins suchas random, block or graft copolymers comprising an α-olefin, e.g.,ethylene or propylene, and at least one compound selected fromα,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid,maleic acid and crotonic acid, and their derivatives such as esters,anhydrides, halides and salts with sodium, potassium, magnesium or zinc;random, block or graft copolymers comprising an α-olefin such asethylene or propylene, and at least one compound selected from vinylacetate, vinyl alcohol and styrenes; copolyamide adhesives andcopolyester adhesives. Of those for the adhesive layer, preferred aremodified polyolefins having a degree of crystallinity, measured throughX-ray diffractiometry, of at most 50%, preferably at most 40% andcontaining from 0.01 to 10% by weight, preferably from 0.05 to 3% byweight of an unsaturated carboxylic acid or its derivative graftedthereon. The adhesive layer of the modified polyolefin that contains anunsaturated carboxylic acid or its derivative within the defined rangeand has a degree of crystallinity falling within the defined range ishighly adhesive to the barrier layer in the multi-layer structure. Thecompounds mentioned hereinabove for the modifying agent for thepolyolefin component (a) are preferred for the unsaturated carboxylicacid and its derivative for the modified polyolefins. Especiallypreferred are unsaturated dicarboxylic acids such as acrylic acid,methacrylic acid; dicarboxylic acid anhydrides such as maleic anhydride,itaconic anhydride; and glycidyl esters of unsaturated carboxylic acidssuch as glycidyl acrylate, glycidyl methacrylate.

[0078] One or more such modified polyolefins may be used for theadhesive layer, either singly or as combined. The modified polyolefinmixtures shall have the degree of crystallinity and the degree ofgrafting each falling within the defined range. The mixtures may containany other graft-modified polyolefins of which the degree ofcrystallinity and/or the degree of grafting overstep the range, and/orpolyolefins not grafted and modified.

[0079] Preferred examples of the polyolefins before grafted and modifiedand those not grafted and modified are homopolymers of α-olefins havingfrom 2 to 20 carbon atoms, and copolymers of two or more different typesof such α-olefins. The α-olefins include, for example, ethylene,propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene,1-tetradecene and 1-octadecene. The polyolefins may be copolymerizedwith minor, for example, at most 10 mol % of any other monomers exceptα-olefins.

[0080] For the polyolefins, especially preferred are ethylenehomopolymers and ethylene-α-olefin random copolymers. Concretely, theyare linear low-density polyethylene (L-LDPE), ethylene-propylenecopolymers, and ethylene-butene copolymers. Of those, more preferred arethe ethylene copolymers having an MFR of from 0.1 to 50 g/10 min,preferably from 0.2 to 20 g/10 min, a density of from 0.850 to 0.940g/cm³, preferably from 0.855 to 0.920 g/cm³, an ethylene content of from30 to 95 mol %, preferably from 40 to 92 mol %, and a degree ofcrystallinity measured through X-ray diffractiometry of at most 50%,preferably at most 40%.

[0081] The modified polyolefins for the adhesive layer may contain atackifier. Concretely, the tackifier includes, for example, aliphatichydrocarbon resins, alicyclic hydrocarbon resins prepared byhydrogenating aromatic hydrocarbon resins, as well as α-pinene resins,terpene resins, rosin, modified rosins, and their mixtures. Thetackifying resins are solid amorphous polymers heretofore used fortackifiers and adhesives in the field of adhesive tapes, coatingcompositions and hot-melt adhesives. Of those, especially preferred foruse herein are alicyclic hydrocarbons having a softening point (in ringand ball method) of from 105 to 150° C., preferably from 110 to 140° C.,and having a degree of hydrogenation of aromatic nuclei of at least 80%,preferably at least 85%. Commercially-available tackifiers are alsousable herein. For example, mentioned is Arakawa Chemical Industry'sArkon P-125.

[0082] The blend ratio of the modified polyolefin and the tackifier maybe such that the modified polyolefin accounts for from 60 to 99% byweight, preferably from 80 to 95% by weight, and the tackifier accountsfor from 1 to 40% by weight, preferably from 5 to 20% by weight.

[0083] For making it electroconductive, the thermoplastic resinstructure of the invention may contain an electroconductive fillerand/or an electroconductive polymer. The additives are not specificallydefined. For example, the electroconductive filler may be any and everyone generally used in ordinary resins for making them electroconductive.Its examples are metal powders, metal flakes, metal ribbons, metalfibers, metal oxides, electroconductive substance-coated inorganicfillers, carbon powder, graphite, carbon fibers, carbon flakes, andscaly carbon.

[0084] Examples of the metal for the metal powders, metal flakes andmetal ribbons are silver, nickel, copper, zinc, aluminium, stainlesssteel, iron, brass, chromium, and tin.

[0085] Examples of the metal for the metal fibers are iron, copper,stainless steel, aluminium, and brass.

[0086] The metal powders, metal flakes, metal ribbons and metal fibersmaybe processed on their surfaces with a surface-treating agent such astitanate-type, aluminium-type or silane-type agents.

[0087] Examples of the metal oxides are (antimony-doped) SnO₂,(antimony-doped) In₂O₃, and (aluminium-doped) ZnO. These may beprocessed on their surfaces with a surface-treating agent such astitanate, aluminium or silane coupling agents.

[0088] Examples of the electroconductive substance for theelectroconductive substance-coated inorganic fillers are aluminium,nickel, silver, carbon, (antimony-doped) SnO₂, and (antimony-doped)In₂O₃. Examples of the inorganic fillers to be coated with it are mica,glass beads, glass fibers, carbon fibers, potassium titanate whiskers,barium sulfate, zinc oxide, titanium oxide, aluminium borate whiskers,zinc oxide whiskers, titanium oxide whiskers, and silicon carbidewhiskers. For coating them, for example, employable are various methodsof vacuum vapor deposition, sputtering, electroless plating or baking.The inorganic fillers may be processed on their surfaces with asurface-treating agent such as titanate, aluminium or silane couplingagents.

[0089] Grouped from its starting materials and production methods,carbon powder includes, for example, acetylene black, gas black, oilblack, naphthalene black, thermal black, furnace black, lamp black,channel black, roll black, and disc black. The carbon powder for use inthe invention is not specifically defined in point of its startingmaterials and production methods. For it, however, especially preferredare acetylene black and furnace black. Produced are various types ofcarbon powder that differ in their characteristic parameters such asparticle size, surface area, DBP oil absorption and ash content. Thecarbon powder for use in the invention is not specifically defined inpoint of its characteristic parameters. However, for good balance ofstrength and electroconductivity thereof, the carbon powder for useherein preferably has a mean particle size of at most 500 nm, morepreferably falling between 5 and 100 nm, even more preferably between 10and 70 nm. The specific surface area (in BET method) of the carbonpowder is preferably at least 10 m²/g, more preferably at least 30 m²g.The DBP oil absorption thereof is preferably at least 50 ml/100 g, morepreferably at least 100 ml/100 g. The ash content thereof is preferablyat most 0.5% by weight, more preferably at most 0.3% by weight.

[0090] The carbon particles may be processed on their surfaces with asurface-treating agent such as titanate-type, aluminium-type orsilane-type agents. For better processability in melt kneading, thecarbon powder maybe formed into granules.

[0091] The moldings obtained by fabricating the thermoplastic resinstructure of the invention are often desired to have good surfacesmoothness. From this viewpoint, desired for the electroconductivefillers for use in the invention are powdery, granular, tabular or flakymatters as well as fibrous matters that have a ratio of length/diameterof at most 200 in the resin composition, rather than fibrous fillershaving a high aspect ratio, like those for the inorganic filler (c) usedin the invention.

[0092] Examples of the electroconductive polymer are polyaniline,polypyrrole, polyacetylene, poly(paraphenylene), polythiophene, andpolyphenylenevinylene.

[0093] Two or more different matters of the electroconductive fillerand/or the electroconductive polymer may be used herein, as combined. Ofthose electroconductive fillers and electroconductive polymers,especially preferred is carbon black as it is strong and inexpensive.

[0094] The content of the electroconductive filler and/or theelectroconductive polymer that may be in the resin structure of theinvention varies, depending on the type of the electroconductive fillerand/or the electroconductive polymer to be used, and therefore could notbe indiscriminately defined. However, from the viewpoint of the balanceof the electroconductivity, the flowability and the mechanical strengthof the resin composition, it is desirable that the filler content of theresin composition falls between 1 and 250 parts by weight, morepreferably between 3 and 100 parts by weight relative to 100 parts byweight of the total of the components (a), (b) and (c). Also morepreferably, the filler content falls between 3 and 100 parts by weightrelative to 100 parts by weight of the total of the components (a) and(b) for well making the resin structure electroconductive.

[0095] Preferably, the electroconductive resin structure has a volumeresistivity of at most 10¹⁰ Ω.cm in order that it is resistant to staticelectrification. However, the electroconductive filler and theelectroconductive polymer, if any in the resin composition, will oftenworsen the flow ability of the composition and the strength of the resinstructure. Therefore, so far as the intended electroconductive level isattained, the amount of the electroconductive filler and theelectroconductive polymer to be in the resin composition is as small aspossible. The intended electroconductive level varies, depending on theuse of the resin structure. In general, the volume resistivity of theresin structure shall be larger than 100 Ω.cm but not larger than 10¹⁰Ω.cm.

[0096] The resin composition of the invention may contain any othercomponents not detracting from the effect of the invention. For example,it may contain any of antioxidants and heat-resistant stabilizers (e.g.,hindered phenols, hydroquinones, phosphites and their substitutedderivatives), weatherproofing agents (e.g., resorcinols, salicylates,benzotriazoles, benzophenones, hindered amines), mold release agents andlubricants (e.g., montanic acid and its metal salts, esters and halfesters; stearyl alcohol, stearamide, various bisamides, bisureas,polyethylene wax), pigments (e.g., cadmium sulfide, phthalocyanine,carbon black) ,dyes (e.g., nigrosine), nucleating agents (e.g., talc,silica, kaolin, clay), plasticizers (e.g., octyl p-hydroxybenzoate,N-butylbenzenesulfonamide), antistatic agents (e.g., alkylsulfate-typeanionic antistatic agents, quaternary ammonium-type cationic antistaticagents, nonionic antistatic agents such as polyoxyethylene sorbitanmonostearate, betaine-type ampholytic antistatic agents), flameretardants (e.g., red phosphorus, melamine cyanurate, hydroxides such asmagnesium hydroxide and aluminium hydroxide, ammonium polyphosphate,polystyrene bromide, polyphenylene ether bromide, polycarbonate bromide,epoxy bromide resin, and combinations of such a bromine-containing flameretardant and antimony trioxide), and other polymers.

[0097] The method for producing the resin structure of the invention isnot specifically defined, so far as the resin structure produced canhave the morphology that satisfies the requirement of the invention. Forrealizing the preferred morphology, for example, the polyolefin resinand the PPS resin to form the resin structure are fed into separate twoextruders through the respective main feeders and an inorganic filler isadded thereto through a side feeder disposed at the top of eachextruder; or the polyolefin resin and the PPS resin are first kneaded inmelt, and an inorganic filler is added to the mixed resin melt.

[0098] The thermoplastic resin structure and the multi-layer structureof the invention may be shaped in any known manner, and the method ofmolding them is not specifically defined, for which, for example,employable is injection molding, extrusion molding, blow molding orpress molding. Especially preferred for molding them is at least onemethod selected from injection molding, injection compression moldingand compression molding for enhancing the productivity and theindustrial application of the invention. The molding temperature mayfall generally within a range higher than the melting point of the PPSresin by from 5 to 50° C. In general, the moldings are single-layered,but may be multi-layered in a two-layer molding method.

[0099] The layer configuration in the multi-layer structure of theinvention is not specifically defined. All the layers of the multi-layerstructure may be formed of the thermoplastic resin structure of theinvention, or any other thermoplastic resin may be used for some layers.In two-layered multi-layer structures, the layer of the thermoplasticresin structure of the invention is preferably the innermost layer inorder that it can fully exhibit its transmission-resistant effect. Themoldings obtained herein may be integrated together or with othermoldings by the use of an adhesive or through hot-sealing, and themethod of integrating them is not specifically defined, for which areemployable any known techniques.

[0100] As the thermoplastic resin structure and the multi-layerstructure of the invention have good gas barrier properties, and aredurable and easy to work, they are favorable for containers fortransportation and/or storage of liquid chemicals and gases, for theattached parts of such containers, and also for multi-layered tubes ormulti-layered blow moldings to be formed through coextrusion. Regardingthe liquid chemicals and the gases, the resin structure and themulti-layer structure are highly resistant to transmission therethroughof vapors and/or liquids and also evaporated gases, for example,Flon-11, Flon-12, Flon-21, Flon-22, Flon-113, Flon-114, Flon-115,Flon-134a, Flon-32, Flon-123, Flon-124, Flon-125, Flon-143a, Flon-141b,Flon-142b, Flon-225, Flon-C318, R-502, 1,1,1-trichloroethane, methylchloride, methylene chloride, ethyl chloride, methylchloroform, propane,isobutane, n-butane, dimethyl ether, castor oil-based brake fluid,glycol ether-based brake fluid, borate-based brake fluid, brake fluidfor use in extremely cold regions, silicone oil-based brake fluid,mineral oil-based brake fluid, power steering oil, windshield wash,gasoline, methanol, ethanol, isobutanol, butanol, nitrogen, oxygen,hydrogen, carbon dioxide, methane, propane, natural gas, argon, helium,xenon and medicines. Therefore, the resin structure and the multi-layerstructure have many applications for parts of electric and electronicappliances, medical appliances, food-related appliances, household andoffice-use appliances, constructions-related parts, furniture parts andothers. For example, their applications are for films of transmissionresistance against vapors and/or liquids mentioned above; as well as fortanks and bottles for automobile parts, parts for medical appliances anddaily commodities, such as air bags, bottles for liquid chemicals suchas shampoo, rinse, liquid soap, detergent, tanks for storage of liquidchemicals, tanks for storage of gases, coolant tanks, oil transportationtanks, disinfectant tanks, tanks for blood transfusion pumps, fueltanks, windshield wash tanks, oil reservoir tanks, canisters; Attachedparts for such tanks and bottles, such as valves, e.g., cutoff valves,joints, gauges for attendant pumps, cases and other parts, various fueltubes and connecting parts (e.g., connectors), e.g., fuel fillerunder-pipes, ORVR hoses, reserve hoses, bent hoses, oil tubes andconnecting parts, brake hoses and connecting parts, windshield washnozzles and hoses, cooler hoses and connecting parts for cooling waterand coolant, tubes and connecting parts for coolant for airconditioners, floor-warming pipes and connecting parts, fireextinguishers and fire hoses, tubes, connecting parts and valves formedical cooling devices, tubes for transportation of liquid chemicalsand gases, containers for storage of liquid chemicals, and otherapplications requiring liquid chemical and vapor transmissionresistance; and machine parts such as automobile parts, internalcombustion engine parts, and housings for electric tools.

EXAMPLES

[0101] The invention is described in detail hereinunder with referenceto Examples. However, the scope of the invention is not limited to onlythe following Examples.

[0102] (1) Alcohol gasoline transmission:

[0103] Using a 40 mmφ extruder with a tubular die, a sizing die to coolthe tube extruded out of the extruder and to control the size of thetube and a take-up unit disposed at its top, a tube having an outerdiameter of 8 mm and an inner diameter of 6 mm was molded. The tube wascut into a length of 20 cm. One end of the sample was sealed up, just 6g of an alcohol gasoline mixture of commercially-available regulargasoline/ethanol of 75/25 by weight was put into it, and the other endthereof was sealed up. With that, the overall weight of the sample wasmeasured. The sample was put into an explosion-proof oven at 60° C., andkept therein for 500 hours, and its weight loss was measured.

[0104] (2) Oxygen transmission:

[0105] Measured according to JIS K7126, method A (differential pressuremethod), for which used was GTR-10 (by Yanako Bunseki Kogyo).

[0106] (3) Mechanical strength:

[0107] Measured according to standard methods mentioned below.

[0108] Tensile strength: ASTM D638

[0109] Flexural modulus: ASTM D790

[0110] Izod impact strength: ASTM D256

[0111] (4) Analysis of separated morphology:

[0112] The cross section (barrier layer) of the molded tube was analyzedwith electronic microscopes (TEM, SEM).

[0113] (5) Physical properties of multi-layer structure:

[0114] (A) Gasohol barrier properties:

[0115] The tube was cut into a length of 30 cm. One end of the samplewas sealed up, an alcohol gasoline mixture of commercially-availableregular gasoline/methyl alcohol of 85/15 (by weight) was put into it,and the other end thereof was sealed up. With that, the overall weightof the sample was measured. The sample was put into an explosion-proofoven at 40° C. From the weight change of the sample, the alcoholgasoline transmission through the tube was determined.

[0116] (B) Interlayer adhesion strength:

[0117] The tube was cut and opened into a rectangular strip having awidth of 10 mm, and the inner and outer layers with an adhesive layertherebetween (the adhesive layer was stuck to the neighboring layer of athermoplastic resin composition) were peeled away by pulling them in theopposite directions at 180 degrees, whereupon the adhesion strength perthe unit length of the sample was measured.

[Reference Example 1 (preparation of PPS copolymer)]

[0118] 3.26 kg of sodium sulfide (25 mols, containing 40% crystalwater), 4 g of sodium hydroxide, 1.36 kg of sodium acetate trihydrate(about 10 mols), and 7.9 kg of N-methylpyrrolidone were fed into anautoclave equipped with a stirrer, and gradually heated up to 205° C.with stirring, and about 1.5 liters of distillate containing 1.36 kg ofwater was removed. To the residual mixture, added were 3.38 kg of1,4-dichlorobenzene (23.0 mols), 0.37 kg of 1,3-dichlorobenzene (2.5mols), and 2 kg of NMP, and heated at 265° C. for 5 hours. The reactionproduct was washed three times with hot water at 70° C., then withaqueous acetic acid solution with pH =4 at 60° C., and further fourtimes with hot water at 70° C., and then dried under reduced pressure at80° C. for 24 hours to obtain about 2 kg of a PPS copolymer resin havinga melting point of 255° C. and MFR of 800 g/10 min (at 315° C. under5000 g).

[0119] The polyolefin resins and PPS used in Examples and ComparativeExamples are mentioned below. Unless otherwise specifically indicated,they were prepared through ordinary polymerization.

[0120] <Polyolefin Resins>

[0121] (PO-1): high-density polyethylene having MFR of 14 and density of0.96.

[0122] (PO-2): high-density polyethylene having MFR of 32 and density of0.96.

[0123] (PO-3): polypropylene having MFR of 10 and density of 0.89.

[0124] (PO-4): high-density polyethylene having MFR of 0.3 and densityof 0.95.

[0125] (PO-5): high-density polyethylene having MFR of 6.0 and densityof 0.96.

[0126] (PO-6): low-density polyethylene having MFR of 1.0 and density of0.92.

[0127] (PO-7): polypropylene having MFR of 0.5 and density-of 0.89.

[0128] (PO-8): ethylene-ethyl acrylate copolymer having MFR of 1.5 anddensity of 0.93.

[0129] (PO-9): ethylene-propylene copolymer having MFR of 0.6 anddensity of 0.88.

[0130] <PPS Resins>

[0131] (PPS-1): PPS resin having melting point of 280° C., MFR of 1000g/10 min (at 315° C. under 5000 g) and weight-average molecular weight(Mw) of 30000.

[0132] (PPS-2): PPS resin having melting point of 280° C., MFR of 300g/10 min, Mw of 49000 and viscosity of 700 poises.

[0133] (PPS-3): PPS resin having melting point of 280° C., MFR of 100g/10 min, Mw of 70000 and viscosity of 1700 poises.

[0134] (PPS-4): PPS resin having melting point of 280° C., MFR of 600g/10 min, Mw of 38000 and viscosity of 450 poises.

[0135] (PPS-5): PPS copolymer resin prepared in Reference Example 1,having melting point of 255° C. and MFR of 800 g/10 min.

[0136] <Thermoplastic resins except resin compositions to form barrierlayer (these are for neighboring layer)>

[0137] (β-1): high-density polyethylene having MFR of 0.3 g/10 min anddensity of 0.94.

[0138] (β-2): polybutylene terephthalate (Toray's LUMI CON 5201X11).

[0139] (β-3): nylon 11 (Toray's RILSAN BESN O P40TL).

[0140] (β-4.): ethylene-1-hexene copolymer having MFR of 4 g/10 min anddensity of 0.92.

[0141] <Resins for adhesive Layer>

[0142] (γ-1): ethylene/glycidyl methacrylate (90/10 wt. %) copolymer.

[0143] (γ-2): ethylene/methyl acrylate/glycidyl methacrylate (64/30/6wt. %) copolymer.

[0144] (γ-3): maleic anhydride-modified ethylene/1-butene copolymer(having density of 0.88, degree of crystallinity of 15%, and degree ofgrafting with maleic anhydride of 0.4% by weight).

[0145] (γ-4): maleic anhydride-modified ethylene/1-octene copolymer(having density of 0.86, degree of crystallinity of 5% or less, anddegree of grafting with maleic anhydride of 0.8% by weight)

[0146] (γ-5): adhesive composition prepared by mixing maleicanhydride-modified ethylene/1-butene copolymer (having density of 0.88,degree of crystallinity of 15%, and degree of grafting with maleicanhydride of 0.4% by weight), maleic anhydride-modified polyethylene(having density of 0.96 and degree of grafting with maleic anhydride of2.0% by weight), and tackifier (Arakawa Chemical Industry's Arkon P-125)were mixed in a ratio of 85/5/10 parts by weight, followed by kneadingthe mixture in melt in a double-screw extruder at a cylinder temperatureof 200° C.

Examples 1 to 15, Comparative Examples 1 to 4

[0147] As in Tables 1 and 2, the mixture previously prepared by meltingand kneading the PPS resin and a compatibilizer (ethylene/glycidylmethacrylate copolymer, 90/10% by weight), and the polyolefin resin werefed into a double-screw extruder, Nippon Seikosho's TEX 30 Model throughits main feeder. The inorganic filler, if used, was fed thereintothrough a side feeder provided at some part of the cylinder. These werekneaded in melt in the extruder at 300° C., for which the screwrevolution was 200 rpm. The resulting pellets were dried, and theninjection-molded into test pieces. The injection-molding machine usedwas Toshiba Kikai's IS100FA, and the mold temperature was 80° C. Inaddition, the pellets prepared in the same manner as above were moldedinto tubes for the test for alcohol gasoline transmission through them.The data of the transmission resistance and the mechanical strength ofthe samples are given in Tables 1 and 2. Some samples were analyzed forthe separated morphology therein. FIG. 4 is the electronmicroscopicpicture of the sample of Example 8; and FIG. 5 is theelectronmicroscopic picture of the sample of Comparative Example 2.

[0148] In the Tables, GF is glass fibers (of 3 mm chopped strands havinga fiber diameter of 10 μm, by Nippon Electric Glass); MF is milledfibers (having a mean fiber length of 140 μm and a mean fiber diameterof 9 μm, by Nippon Electric Glass). TABLE 1 Item Unit Ex. 1 Ex. 2 Ex.3Ex. 4 Ex. 5 Constituent Type of polyolefin resin — PO-1 PO-2 PO-1 PO-3PO-1 Components amount vol. % 67 56 78 62 67 Type of PPS resin — PPS-2PPS-1 PPS-1 PPS-1 PPS-1 amount vol. % 30 40 20 35 30 Compatibilizer vol.% 3 4 2 3 3 Separated Morphology continuous PPS PPS and polyolefin PPSPPS and phase polyolefin matrix polyolefin matrix disperse polyolefin —PPS polyolefin — phase laminar dispersion Transmission alcohol gasolineg 0.5 0.7 0.8 0.6 0.6 Resistance transmission oxygen note 1 40 60 80 4050 transmission Mechanical tensile strength MPa 45 55 40 60 45 Strengthflexural modulus GPa 2.2 2.5 2.0 2.6 2.0 Izod impact J/m 50 56 44 42 45strength Co. Co. Item Unit Ex. 6 Ex. 7 Ex. 8 Ex. 1 Ex. 2 ConstituentType of polyolefin resin — PO-1 PO-4 PO-4 PO-1. PO-2 Components resinamount vol. % 34 57 69 100 67 Type of PPS resin — PPS-2 PPS-1 PPS-2 —PPS-3 amount vol. % 60 40 30 30 Compatibilizer vol. % 6 3 1 — 3Separated Morphology continuous PPS and polyolefin polyolefin polyolefinpolyolefin phase polyolefin matrix disperse — PPS PPS — PPS phaselaminar laminar spherical dispersion dispersion dispersion Transmissionalcohol gasoline g 0.4 0.5 0.7 3.3 2.8 Resistance transmission oxygennote 1 15 50 90 10000 9000 transmission Mechanical tensile strength MPa70 40 35 30 35 Strength flexural modulus GPa 2.7 2.0 1.7 1.0 1.5 Izodimpact J/m 40 50 46 30 28 strength

[0149] TABLE 2 Item Unit Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 ConstituentType of polyolefin resin — PO-1 PO-2 PO-1 PO-3 PO-1 Components amountvol. % 67 56 78 62 67 Type of PPS resin — PPS-2 PPS-1 PPS-1 PPS-1 PPS-1amount vol. % 30 40 20 35 30 Compatibilizer vol. % 3 4 2 3 3 Type ofinorganic filler — GF GF GF GF/talc GF/MF amount wt. % 40 40 40 35/530/10 Separated continuous PPS PPS and polyolefin PPS PPS and Morphologyphase polyolefin polyolefin matrix disperse polyolefin — PPS polyolefin— phase laminar dispersion Transmission alcohol gasoline g 0.4 0.6 0.70.5 0.6 Resistance transmission oxygen transmission note 1 40 60 70 4050 Mechanical tensile strength MPa 110 110 100 95 90 Strength flexuralmodulus GPa 6.3 7.0 6.1 5.5 5.2 Izod impact J/m 90 100 95 90 85 strengthItem Unit Ex. 14 Ex. 15 Co. Ex. 3 Co. Ex. 4 Constituent Type ofpolyolefin resin — PO-1 PO-4 PO-1 PO-2 Components amount vol. % 34 58100 67 Type of PPS resin — PPS-2 PPS-2 — PPS-3 amount vol. % 60 40 30Compatibilizer vol. % 6 2 — 3 Type of inorganic filler — GF GF GF GFamount wt. % 40 40 40 40 Separated Morphology continuous PPS andpolyolefin polyolefin polyolefin phase polyolefin matrix disperse — PPS— PPS phase laminar spherical dispersion dispersion Transmission alcoholgasoline g 0.3 0.6 3.2 2.5 Resistance transmission oxygen transmissionnote 1 10 60 10000 9000 Mechanical tensile strength MPa 115 100 100 110Strength flexural modulus GPa 7.8 7.3 5.4 6.0 Izod impact J/m 100 100 9080 strength

[0150] As in Examples 1 to 15 and Comparative Examples 1 to 4, the resinmoldings of the invention having a specific, separated morphology asdefined herein have good transmission resistance and confirmed thepractical applicability of the resin structure of the invention. Inaddition, the test pieces formed through injection moldings also havegood transmission resistance and confirmed the practical applicabilityof the resin structure of the invention.

Examples 16 to 32, Comparative Examples 5 to 8

[0151] As in Tables 3 to 5, the PPS resin was mixed with acompatibilizer (ethylene/glycidyl methacrylate copolymer, 90/10% byweight), the resulting mixture was fed into a double-screw extruder,Nippon Seikosho's TEX 30 Model through its main feeder with thepolyolefin resin being thereinto through a side feeder provided at somepart of the cylinder, and these were kneaded in melt at 270 to 300° C.,for which the screw revolution was 200 rpm. The resulting pellets weredried, and then molded into tubes.

[0152] In that manner, molded were three-resin three-layer tubescomposed of one barrier layer (α), one neighboring layer (β) ofthermoplastic resin, and one adhesive layer (γ) between the barrierlayer and the neighboring layer (or two-resin two-layer tubes not havingthe adhesive layer). For these, the molding machine used has threeextruders, a forming die, a sizing die and a take-up unit, in which theresin melts extruded out of the three extruders are collected in anadapter and molded into a tube through the forming die, and the tube iscooled and its size is controlled by the sizing die.

[0153] The three-layer tubes obtained herein had an outer diameter of 8mm and an inner diameter of 6 mm, in which the thickness of the outerlayer (thermoplastic resin layer) was 0.70 mm (in the two-layer tubes,however, this was 0.80 mm), that of the adhesive layer was 0.10 mm andthat of the inner layer (barrier layer) was 0.20 mm. The multi-layertubes were tested, and the test results are given in Tables 3, 4 and 5.TABLE 3 Item Unit Ex. 16 Ex. 17 Ex. 18 Co. Ex. 5 Constituent Type ofpolyolefin resin (a) — PO-4 PO-5 PO-5 — Components of Amount ofpolyolefin resin vol. % 65 50 77 Barrier Type of PPS resin (b) — PPS-4PPS-4 PPS-3 PPS-3 Layer (α) Amount of PPS resin vol. % 30 45 20 100Compatibilizer vol. % 5 5 3 — Layer (β) Thermoplastic resin β-1 β-1 β-1β-1 layer (neighboring layer) Layer (γ) Adhesive layer γ-1 γ-1 γ-1 γ-1Separated Morphology continuous PPS PPS and PPS laminar PPS of BarrierLayer phase polyolefin dispersion disperse polyolefin — PPS laminar —phase dispersion Gasohol gasohol transmission 0.67 0.75 0.89 0.24Barrier (g · mm/m² · 24 h · atm) Properties Interlayer Adhesion Strength3.1 3.5 4.2 0.5 or less of Moldings (kg/10 mm) Item Unit Co. Ex. 6 Co.Ex. 7 Co. Ex. 8 Constituent Type of polyolefin resin (a) — PO-5 PO-5PO-4 Components of Amount of polyolefin resin vol. % 70 70 100 BarrierType of PPS resin (b) — PPS-3 PPS-3 — Layer (α) Amount of PPS resin vol.% 25 25 Compatibilizer vol. % 5 5 — Layer (β) Thermoplastic resin β-1β-1 β-1 layer (neighboring layer) Layer (γ) Adhesive layer γ-1 — γ-1Separated Morphology continuous polyolefin polyolefin polyolefin ofBarrier Layer phase disperse PPS spherical PPS spherical — phasedispersion dispersion Gasohol gasohol transmission 10 or more 10 or more10 or more Barrier (g · mm/m² · 24 h · atm) Properties InterlayerAdhesion Strength not peeled 2.2 not peeled of Moldings (kg/10 mm)

[0154] TABLE 4 Item Unit Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24Constituent Type of polyolefin resin (a) — PO-6 PO-7 PO-8 PO-9 PO-4 PO-4Components Amount of polyolefin resin vol. % 40 80 55 77 65 65 ofBarrier Type of PPS resin (b) — PPS-4 PPS-5 PPS-5 PPS-5 PPS-5 PPS-4Layer (α) Amount of PPS resin vol. % 60 15 40 20 30 30 Compatibilizervol. % 5 5 5 3 5 5 Layer (β) Thermoplastic resin layer β-1 β-1 β-2 β-3β-2 β-3 (neighboring layer) Layer (γ) Adhesive layer γ-1 γ-1 γ-1 γ-2 γ-1γ-2 Separated Morphology continuous PPS polyolefin PPS and PPS and PPSPPS of Barrier Layer phase polyolefin polyolefin disperse polyolefin PPSlaminar — — polyolefin polyolefin phase dispersion Gasohol gasoholtransmission 0.54 0.82 0.63 0.75 0.70 0.56 Barrier (g · mm/m² · 24 h ·atm) Properties Interlayer Adhesion Strength 2.6 4.7 4.5 4.4 3.9 3.8 ofMoldings (kg/10 mm)

[0155] TABLE 5 Item Unit Ex. 25 Ex. 26 Ex. 27 Ex. 28 Constituent Type ofpolyolefin resin (a) — PO-5 PO-4 PO-4 PO-4 Components Amount ofpolyolefin resin vol. % 62 65 65 65 of Barrier Type of PPS resin (b) —PPS-4 PPS-4 PPS-4 PPS-4 Layer (α) Amount of PPS resin vol. % 35 30 30 30Compatibilizer vol. % 3 5 5 5 Layer (β) Thermoplastic resin β-1 β-1 β-1β-1 layer (neighboring layer) Layer (γ) Adhesive layer — γ-3 γ-4 γ-5Separated Morphology continuous polyolefin PPS PPS PPS of Barrier Layerphase disperse PPS laminar polyolefin polyolefin polyolefin phasedispersion Gasohol Barrier gasohol transmission 0.75 0.69 0.70 0.68Properties (g · mm/m² · 24 h · atm) Interlayer Adhesion Strength 2.0 5.25.0 not of Moldings (kg/10 mm) peeled Item Unit Ex. 29 Ex. 30 Ex. 31 Ex.32 Constituent Type of polyolefin resin (a) — PO-5 PO-5 PO-4 PO-4Components Amount of polyolefin resin vol. % 50 77 65 65 of Barrier Typeof PPS resin (b) — PPS-4 PPS-3 PPS-5 PPS-4 Layer (α) Amount of PPS resinvol. % 45 20 30 30 Compatibilizer vol. % 5 3 5 5 Layer (β) Thermoplasticresin β-4 β-4 β β-3 layer (neighboring layer) Layer (γ) Adhesive layerγ-3 γ-5 γ-5 γ-5 Separated Morphology continuous PPS and polyolefin PPSPPS of Barrier Layer phase polyolefin disperse — PPS laminar polyolefinpolyolefin phase dispersion Gasohol Barrier gasohol transmission 0.760.89 0.71 0.57 Properties (g · mm/m² · 24 h · atm) Interlayer AdhesionStrength not not not not of Moldings (kg/10 mm) peeled peeled peeledpeeled

[0156] The multi-layer structures obtained in Examples 16 to 32, whichhave a separated morphology defined in the invention, have good gasoholbarrier properties and good interlayer adhesiveness, and their practicalapplicability is good. In addition, the structures obtained in theseExamples were fabricated into multi-layer blow moldings, and they hadgood properties.

Industrial Applicability

[0157] The thermoplastic resin structure of the invention has good vaporand/or liquid barrier properties, and has many applications in variousfields. For example, it is favorable for electric and electronicappliances-related devices, precision machines-related devices,office-use appliances, automobiles and trains-related parts, buildingmaterials, wrapping and packaging materials, furniture, and dailynecessaries. In addition, the multi-layer structure of the invention hasgood barrier properties against gasohol, and gives plastic containersand tubes having the advantages of strength, durability and workability.It is favorable for gasoline tanks for automobiles, containers and pipesfor transportation and storage of liquid chemicals, and wrapping andpackaging materials and containers for foods and medicines.

1. A thermoplastic resin structure formed of a resin composition thatcomprises substantially (a) from 5 to 80% by volume of a polyolefinresin and (b) from 20 to 95% by volume of a polyphenylene sulfide resin,which is characterized in that, in morphology therein seen throughelectronic microscopy, the polyphenylene sulfide resin (b) forms amatrix phase (continuous phase) and the polyolefin resin (a) forms adisperse phase.
 2. The thermoplastic resin structure as claimed in claim1, for which the blend ratio of the polyolefin resin (a) and thepolyphenylene sulfide resin (b) is such that the former accounts forfrom 55 to 80% by volume and the latter for from 20 to 45% by volume. 3.The thermoplastic resin structure as claimed in claim 1, for which theblend ratio of the polyolefin resin (a) and the polyphenylene sulfideresin (b) is such that the former accounts for from 60 to 75% by volumeand the latter for from 25 to 40% by volume.
 4. A thermoplastic resinstructure formed of, a resin composition that comprises (a) from 15 to85% by volume of a polyolefin resin and (b) from 15 to 85% by volume ofa polyphenylene sulfide resin, which is characterized in that, inmorphology therein seen through electronic microscopy, both the phase ofthe polyphenylene sulfide resin (b) and the phase of the polyolefinresin (a) are substantially continuous phases.
 5. A thermoplastic resinstructure formed of a resin composition that comprises (a) from 55 to95% by volume of a polyolefin resin and (b) from 5 to 45% by volume of apolyphenylene sulfide resin, which is characterized in that, inmorphology therein seen through electronic microscopy, the polyolefinresin (a) forms a continuous phase and the polyphenylene sulfide resin(b) forms a laminar disperse phase.
 6. The thermoplastic resin structureas claimed in any of claims 1 to 5, for which the polyolefin resin (a)is at least one selected from polyethylene, polypropylene,ethylene/α-olefin copolymers, [copolymers of (ethylene and/or propylene)and (unsaturated carboxylic acid and/or unsaturated carboxylate)], and[copolymers of (ethylene and/or propylene) and (unsaturated carboxylicacid and/or unsaturated carboxylate) in which at least a part of thecarboxyl groups are modified into metal salts].
 7. The thermoplasticresin structure as claimed in any of claims 1 to 6, which contains (c)from 0.5 to 200 parts by weight, relative to 100 parts by weight of thetotal of the polyolefin resin (a) and the polyphenylene sulfide resin(b), of an inorganic filler.
 8. Containers for transportation or storageof liquid chemicals or gases, which are obtained by working thethermoplastic resin structure of any of claims 1 to
 7. 9. Attached partsfor containers for transportation or storage of liquid chemicals orgases, which are obtained by working the thermoplastic resin structureof any of claims 1 to
 7. 10. Moldings of the thermoplastic resinstructure of any of claims 1 to 7, which are formed in at least onemethod of injection molding, injection compression molding orcompression molding.
 11. A multi-layer structure with a barrier layer,in which the barrier layer is formed of the thermoplastic resinstructure of any of claims 1 to
 7. 12. The multi-layer structure asclaimed in claim 11, wherein a neighboring layer is formed on one orboth surfaces of the barrier layer, and the neighboring layer is athermoplastic resin layer differing from the thermoplastic resinstructure that forms the barrier layer.
 13. The multi-layer structure asclaimed in claim 12, wherein the thermoplastic resin to form theneighboring layer is at least one selected from polyolefin resins,thermoplastic polyester resins, polyamide resins, polycarbonate resinsand ABS resins.
 14. The multi-layer structure as claimed in claim 12,wherein the thermoplastic resin to form the neighboring layer is atleast one selected from polyolefin resins, thermoplastic polyesterresins and polyamide resins.
 15. The multi-layer structure as claimed inclaim 12, wherein the thermoplastic resin to form the neighboring layeris an ethylene homopolymer and/or an ethylene/α-olefin copolymer havinga melt flow rate of from 0.01 to 30 g/10 min and a density of from 0.90to 0.97 g/cm³.
 16. The multi-layer structure as claimed in claim 12,which has an adhesive layer formed between the barrier layer and theneighboring layer.
 17. The multi-layer structure as claimed in claim 16,wherein the adhesive layer is formed of a modified polyolefin having adegree of crystallinity of at most 50% and containing from 0.01 to 10%by weight of an unsaturated carboxylic acid or its derivative graftedthereon.
 18. The multi-layer structure as claimed in claim 17, whereinthe adhesive layer comprises from 60 to 99 parts by weight of a modifiedpolyolefin having a degree of crystallinity of at most 50% andcontaining from 0.01 to 10% by weight of an unsaturated carboxylic acidor its derivative grafted thereon, and from 1 to 40 parts by weight of atackifier.
 19. The multi-layer structure of as claimed in any of claims11 to 18, which is formed through coextrusion.
 20. The multi-layerstructure as claimed in any of claims 11 to 19, which is formed intomulti-layered tubes or multi-layered blow moldings through coextrusion.